CN104529006A - Device capable of reducing acidity and moisture of dichloromethane waste liquid - Google Patents
Device capable of reducing acidity and moisture of dichloromethane waste liquid Download PDFInfo
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- CN104529006A CN104529006A CN201410839326.3A CN201410839326A CN104529006A CN 104529006 A CN104529006 A CN 104529006A CN 201410839326 A CN201410839326 A CN 201410839326A CN 104529006 A CN104529006 A CN 104529006A
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Abstract
The invention relates to a device capable of reducing acidity and moisture of a dichloromethane waste liquid and belongs to the technical field of recovery of the dichloromethane waste liquid. A raw material storage tank of the device is respectively connected with a first solid alkali fixed bed, a second solid alkali fixed bed and a water absorbent fixed bed through a circulation pump by virtue of control valves; a finished product storage tank is connected with the water absorbent fixed bed by virtue of a control valve; and an on-line acidity detector is connected with the raw material storage tank. A solid alkali-loaded mesoporous molecular sieve SBA-15, which is adopted in the device, has the large specific surface area and good hydrothermal stability, can be in full contact with acidic substances in the dichloromethane waste liquid and can be regenerated, and thus the utilization efficiency of the solid alkali-loaded mesoporous molecular sieve SBA-15 is increased. By mixing nanometer calcium carbonate in the process for preparing the solid alkali-loaded mesoporous molecular sieve SBA-15, the acidity-reducing performance of the molecular sieve SBA-15 can be improved.
Description
Technical field
The present invention relates to a kind of device reducing methylene dichloride waste liquid acidity and moisture, belong to methylene dichloride devil liquor recovery technical field.
Background technology
Methylene dichloride has good solvency power, is little, the non-flame properties low boiling point solvent of conventional industrial solvent poisonings, and all having good dissolving power to a lot of resin, paraffin, fat, is a kind of broad-spectrum industrial solvent.The pH of methylene dichloride should in neutral.If the acidity of methylene dichloride is too high, methylene dichloride effect in actual applications can be affected, also can cause corrosion to storage and production unit simultaneously.
The acidic substance of current removal technical grade methylene dichloride mainly adopt sodium hydroxide method, neutralize acidic substance wherein by sodium hydroxide, reach the acidity reducing methylene dichloride.The methylene dichloride of technical grade removes the acidic substance in methylene dichloride by particulate state or flaky sodium hydrate, after the acidic substance in sodium hydroxide and in methylene dichloride, can only go out of use or use for other purposes after sodium hydroxide uses.
And relevant report is had no to acidity in methylene dichloride waste liquid and the higher problem of moisture.Therefore be necessary to adopt a kind of effectively stable method to reduce acidity in methylene dichloride waste liquid and moisture, thus reduce methylene dichloride waste liquid because the problem of acidity and moisture goes out of use and causes waste.
Summary of the invention
For the methylene dichloride waste liquid acidity existed in background technology and the high problem of moisture content, the invention provides a kind of device reducing methylene dichloride waste liquid acidity and moisture.The present invention removes the acidic substance in methylene dichloride waste liquid by kind of solid alkali, thus reduces the acidity of methylene dichloride, reduces the moisture in methylene dichloride waste liquid by water-retaining agent simultaneously.
The technical scheme realizing the object of the invention is: a kind of device reducing methylene dichloride waste liquid acidity and moisture, and this device comprises raw material storage tank, the first solid alkali fixed bed, the second solid alkali fixed bed, water-retaining agent fixed bed, finished product storage tank, online acidity detector and recycle pump; Described raw material storage tank is connected with water-retaining agent fixed bed respectively at the first solid alkali fixed bed, the second solid alkali fixed bed by by-pass valve control through recycle pump; Described finished product storage tank is connected with water-retaining agent fixed bed by by-pass valve control; Described online acidity detector is connected with raw material storage tank.
First solid alkali fixed bed of the present invention and the second solid alkali fixed bed are selected solid alkali to be carried on mesoporous molecular sieve SBA-15 and are processed, and treatment temp is 30 ~ 90 DEG C, and volume space velocity is 1 ~ 10 h
-1, best treatment temp is 50 ~ 70 DEG C, and volume space velocity preferably controls at 3 ~ 6 h
-1.
Preferably, solid alkali of the present invention is carried on mesoporous molecular sieve SBA-15, it is obtained by following steps: 1) be immersed in alkaline solution by mesoporous molecular sieve SBA-15, steeped overnight at room temperature, at a normal, described mesoporous molecular sieve SBA-15 and the mass volume ratio of alkaline solution are (2 ~ 4g): 2mL, and the concentration of alkaline solution is 0.1 ~ 0.5mol/L; 2) in 95 DEG C of water bath with thermostatic control evaporates to dryness, be placed on dry 6 h in 120 DEG C of baking ovens, roasting in retort furnace after oven dry, 10 DEG C/min rises to 550 DEG C, and keeps 3 h, obtains solid alkali and is carried on mesoporous molecular sieve SBA-15.
Described alkaline solution is hydroxide salt, nitrate or carbonate solution, and described hydroxide salt is one or both in sodium hydroxide, potassium hydroxide; Described nitrate is one or both in magnesium nitrate, saltpetre or SODIUMNITRATE; Described carbonate is one or both in sodium carbonate, salt of wormwood.
Further preferably, the present invention also comprises the step of mixing nano-calcium carbonate, namely be immersed in alkaline solution process at mesoporous molecular sieve SBA-15, add nano-calcium carbonate and polyvinyl alcohol more simultaneously, high-speed stirring 30 ~ 60min, the mass ratio of described nano-calcium carbonate, polyvinyl alcohol and mesoporous molecular sieve SBA-15 is (0.2 ~ 0.6): (0.05 ~ 0.1): 1.
More preferably, water-retaining agent fixed bed of the present invention is filled with the water-retaining agent obtained by following steps, concrete preparation process is: 1) be initiator with Potassium Persulphate, N, N '-methylene-bisacrylamide is linking agent, fibroin and kaolin, vinylformic acid, acrylamide are raw material, carry out graft copolymerization with water solution polymerization process and obtain water-retaining agent, temperature of reaction is 50 DEG C, polymerization reaction time is 3 h, 2) water-retaining agent obtained is placed in the methanol aqueous solution of 50%, with sodium hydroxide neutralization, clean and dry.This water-retaining agent is particulate state, and its particle diameter is 3 ~ 5mm.
Wherein, described Potassium Persulphate, N, the mass ratio of N '-methylene-bisacrylamide and fibroin is (0.05 ~ 0.2): (0.1 ~ 0.3): 1, and the mass ratio of described fibroin and kaolin, vinylformic acid, acrylamide is 1:(0.4 ~ 0.6): (3 ~ 5): (1 ~ 3).
The present invention is relative to prior art, and its advantage is:
1) the present invention adopts parallel solid alkali fixed bed to reduce the acidity in methylene dichloride waste liquid, improves the treatment capacity of methylene dichloride waste liquid.When carrying out regeneration step, two solid alkali fixed bed devices that the present invention is arranged can be used alternatingly, thus can carry out the process of serialization to methylene dichloride waste liquid.
2) after having carried out acidity process operation, then carry out water suction step, thus make methylene dichloride reach the use standard of technical grade.
3) requirement of the present invention to equipment is low, and corrodibility is little, while reducing production cost power consumption, allows the mode of production simplify widely, and pollution-free, economic benefit improves.
4) the loaded mesoporous molecular sieve SBA-15 of solid alkali of the present invention's employing, its specific surface area is large, hydrothermally stable is good, fully can contact with the acidic substance in methylene dichloride waste liquid, the loaded mesoporous molecular sieve SBA-15 of solid alkali can regenerate, thus improves the loaded mesoporous molecular sieve SBA-15 utilising efficiency of solid alkali.
5) the present invention is preparing the nano-calcium carbonate mixed in the loaded mesoporous molecular sieve SBA-15 process of solid alkali, can further improve the performance that it reduces acidity.
6) kaolin selected of the present invention and fibroin, can reduce the monomer remnants amount of vinylformic acid in water-absorbing resin, acrylamide.Particularly kaolinic existence removes the effect of colourity in addition.Composite water absorbing agent of the present invention has strong absorptive, the cycle can be utilized long, raw materials wide material sources.
Accompanying drawing explanation
Fig. 1 is setting drawing of the present invention.
In figure, 1, raw material storage tank; 2, the first solid alkali fixed bed; 3, the second solid alkali fixed bed; 4, composite water absorbing agent fixed bed; 5, finished product storage tank; 6, online acidity detector; 7, recycle pump.
Embodiment
Below in conjunction with drawings and Examples the present invention done and describe further.
A kind of device reducing methylene dichloride waste liquid acidity and moisture of the present invention, it comprises raw material storage tank 1, first solid alkali fixed bed 2, second solid alkali fixed bed 3, water-retaining agent fixed bed 4, finished product storage tank 5, online acidity detector 6 and recycle pump 7.Raw material storage tank 1 is connected with water-retaining agent fixed bed 4 respectively at the first solid alkali fixed bed 2, second solid alkali fixed bed 3 by by-pass valve control through recycle pump 7; Finished product storage tank 5 is connected with water-retaining agent fixed bed 4 by by-pass valve control; Online acidity detector 6 is connected with raw material storage tank 1.
The below of the first solid alkali fixed bed 2, second solid alkali fixed bed 3 of the present invention and water-retaining agent fixed bed 4 is respectively equipped with variable valve.
Technical process of the present invention is as follows:
To squeeze in the first solid alkali fixed bed 2 and the second solid alkali fixed bed 3 by recycle pump 7 through pretreated methylene dichloride waste liquid, and flow back in raw material storage tank 1, the methylene dichloride acidity in raw material storage tank 1 is detected by online acidity detector 6, as do not reached technical grade standard, continued to squeeze in the first solid alkali fixed bed 2 and the second solid alkali fixed bed 3 by recycle pump 7, until the acidity value that online acidity detector 6 detects reaches the acidity requirements that technical grade standard specifies, now close the imported valve of the first solid alkali fixed bed 2 and the second solid alkali fixed bed 3, methylene dichloride in raw material storage tank 1 carries out by recycle pump 7 dozens of water-retaining agent fixed beds 4 moisture removed in methylene dichloride that absorbs water, then gravity flow enters finished product and fills with 5.
embodiment 1
Solid alkali is carried on the preparation of mesoporous molecular sieve SBA-15: it is in 0.3mol/L magnesium nitrate solution that 30 g mesoporous molecular sieve SBA-15s are immersed in 20 mL concentration, steeped overnight at room temperature, at a normal; In 95 DEG C of water bath with thermostatic control evaporates to dryness, be placed on dry 6 h in 120 DEG C of baking ovens, roasting in retort furnace after oven dry, 10 DEG C/min rises to 550 DEG C, and keeps 3 h.Investigate and adopt different treatment temps to the treatment effect of methylene dichloride waste liquid acidity, air speed controls at 4 ~ 5 h
-1, treatment effect is specifically in table 1.
Table 1
embodiment 2
Solid alkali is carried on the preparation of mesoporous molecular sieve SBA-15: it is in 0.1mol/L potassium hydroxide solution that 20 g mesoporous molecular sieve SBA-15s are immersed in 20 mL concentration, steeped overnight at room temperature, at a normal; In 95 DEG C of water bath with thermostatic control evaporates to dryness, be placed on dry 6 h in 120 DEG C of baking ovens, roasting in retort furnace after oven dry, 10 DEG C/min rises to 550 DEG C, and keeps 3 h.Investigate and adopt different air speeds to the treatment effect of methylene dichloride waste liquid acidity, treatment temp is 60 DEG C, and treatment effect is specifically in table 2.
Table 2
embodiment 3
Solid alkali is carried on the preparation of mesoporous molecular sieve SBA-15: it is in 0.5mol/L sodium carbonate solution that 40 g mesoporous molecular sieve SBA-15s are immersed in 20 mL concentration, steeped overnight at room temperature, at a normal; In 95 DEG C of water bath with thermostatic control evaporates to dryness, be placed on dry 6 h in 120 DEG C of baking ovens, roasting in retort furnace after oven dry, 10 DEG C/min rises to 550 DEG C, and keeps 3 h.
embodiment 4
In order to improve the processing power of solid alkali further, being carried at solid alkali in the preparation process of mesoporous molecular sieve SBA-15 and can also mixing nano-calcium carbonate.
It is in 0.5mol/L sodium carbonate solution that 40 g mesoporous molecular sieve SBA-15s are immersed in 20 mL concentration, adds 12 g nano-calcium carbonates and 2.4 g polyvinyl alcohol, high-speed stirring 30min, at room temperature, at a normal steeped overnight simultaneously; In 95 DEG C of water bath with thermostatic control evaporates to dryness, be placed on dry 6 h in 120 DEG C of baking ovens, roasting in retort furnace after oven dry, 10 DEG C/min rises to 550 DEG C, and keeps 3 h.
Investigate the treatment effect of embodiment 3 and 4 pairs of methylene dichloride waste liquid acidity, treatment temp is 60 DEG C, and air speed selects 6h
-1, 8h
-1with 10 h
-1, treatment effect is specifically in table 3.
Table 3
embodiment 5
The preparation of water-retaining agent: 1) get Potassium Persulphate 1g, N, N '-methylene-bisacrylamide 2 g, fibroin 10 g and kaolin 5 g, vinylformic acid 40 g, acrylamide 20 g, carry out graft copolymerization with water solution polymerization process and obtain water-retaining agent, temperature of reaction is 50 DEG C, and polymerization reaction time is 3 h, 2) water-retaining agent obtained is placed in the methanol aqueous solution of 50%, neutralize with sodium hydroxide, clean and dry, obtained water-retaining agent is carried out granulation, and its particle diameter is 3 ~ 5mm.
On the basis of embodiment 4, continue the treatment effect investigating embodiment 5 pairs of methylene dichloride waste liquid moisture, air speed is 6 h
-1, effect is specifically in table 4.
Table 4
Claims (9)
1. reduce a device for methylene dichloride waste liquid acidity and moisture, it is characterized in that: this device comprises raw material storage tank (1), the first solid alkali fixed bed (2), the second solid alkali fixed bed (3), water-retaining agent fixed bed (4), finished product storage tank (5), online acidity detector (6) and recycle pump (7); Described raw material storage tank (1) is connected with water-retaining agent fixed bed (4) respectively at the first solid alkali fixed bed (2), the second solid alkali fixed bed (3) by by-pass valve control through recycle pump (7); Described finished product storage tank (5) is connected with water-retaining agent fixed bed (4) by by-pass valve control; Described online acidity detector (6) is connected with raw material storage tank (1).
2. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 1, it is characterized in that: the first described solid alkali fixed bed (2) and the second solid alkali fixed bed (3) are selected solid alkali to be carried on mesoporous molecular sieve SBA-15 and processed, treatment temp is 30 ~ 90 DEG C, and volume space velocity is 1 ~ 10 h
-1.
3. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 2, it is characterized in that: described solid alkali is carried on mesoporous molecular sieve SBA-15, it is obtained by following steps: 1) be immersed in alkaline solution by mesoporous molecular sieve SBA-15, steeped overnight at room temperature, at a normal, described mesoporous molecular sieve SBA-15 and the mass volume ratio of alkaline solution are (2 ~ 4g): 2mL, and the concentration of alkaline solution is 0.1 ~ 0.5 mol/L; 2) in 95 DEG C of water bath with thermostatic control evaporates to dryness, be placed on dry 6 h in 120 DEG C of baking ovens, roasting in retort furnace after oven dry, 10 DEG C/min rises to 550 DEG C, and keeps 3 h, obtains solid alkali and is carried on mesoporous molecular sieve SBA-15.
4. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 3, it is characterized in that: described alkaline solution is hydroxide salt, nitrate or carbonate solution, described hydroxide salt is one or both in sodium hydroxide, potassium hydroxide; Described nitrate is one or both in magnesium nitrate, saltpetre or SODIUMNITRATE; Described carbonate is one or both in sodium carbonate, salt of wormwood.
5. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 3 or 4, it is characterized in that: also comprise the step of mixing nano-calcium carbonate, namely be immersed in alkaline solution process at mesoporous molecular sieve SBA-15, add nano-calcium carbonate and polyvinyl alcohol more simultaneously, high-speed stirring 30 ~ 60min, the mass ratio of described nano-calcium carbonate, polyvinyl alcohol and mesoporous molecular sieve SBA-15 is (0.2 ~ 0.6): (0.05 ~ 0.1): 1.
6. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to Claims 2 or 3, is characterized in that: described treatment temp is 50 ~ 70 DEG C, and volume space velocity is 3 ~ 6 h
-1.
7. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 1, it is characterized in that: described water-retaining agent fixed bed (4) is filled with the water-retaining agent obtained by following steps, concrete preparation process is: 1) be initiator with Potassium Persulphate, N, N '-methylene-bisacrylamide is linking agent, fibroin and kaolin, vinylformic acid, acrylamide is raw material, carry out graft copolymerization with water solution polymerization process and obtain water-retaining agent, temperature of reaction is 50 DEG C, polymerization reaction time is 3 h, 2) water-retaining agent obtained is placed in the methanol aqueous solution of 50%, neutralize with sodium hydroxide, clean and dry.
8. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 7, it is characterized in that: described Potassium Persulphate, N, the mass ratio of N '-methylene-bisacrylamide and fibroin is (0.05 ~ 0.2): (0.1 ~ 0.3): 1, and the mass ratio of described fibroin and kaolin, vinylformic acid, acrylamide is 1:(0.4 ~ 0.6): (3 ~ 5): (1 ~ 3).
9. a kind of device reducing methylene dichloride waste liquid acidity and moisture according to claim 7 or 8, is characterized in that: described water-retaining agent is particulate state, and its particle diameter is 3 ~ 5mm.
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| CN201410839326.3A CN104529006B (en) | 2014-12-30 | 2014-12-30 | A kind of device reducing dichloromethane waste liquid acidity and moisture |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830016A (en) * | 2016-12-30 | 2017-06-13 | 浙江大洋生物科技集团股份有限公司 | The waste liquid containing potassium produced using synthesizing fungicide Difenoconazole produces high pure nitric acid potassium method |
| CN114057541A (en) * | 2021-12-09 | 2022-02-18 | 河南省化工研究所有限责任公司 | Refining and recycling method for dehydration of waste dichloromethane by virtue of supergravity coupling membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451619A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Y-shaped molecular sieve film and removal method for moisture in dichloromethane |
| CN102643156A (en) * | 2012-04-11 | 2012-08-22 | 天津林圣金海化工有限公司 | Chloroethane purification process |
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2014
- 2014-12-30 CN CN201410839326.3A patent/CN104529006B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451619A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Y-shaped molecular sieve film and removal method for moisture in dichloromethane |
| CN102643156A (en) * | 2012-04-11 | 2012-08-22 | 天津林圣金海化工有限公司 | Chloroethane purification process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830016A (en) * | 2016-12-30 | 2017-06-13 | 浙江大洋生物科技集团股份有限公司 | The waste liquid containing potassium produced using synthesizing fungicide Difenoconazole produces high pure nitric acid potassium method |
| CN114057541A (en) * | 2021-12-09 | 2022-02-18 | 河南省化工研究所有限责任公司 | Refining and recycling method for dehydration of waste dichloromethane by virtue of supergravity coupling membrane |
| CN114057541B (en) * | 2021-12-09 | 2023-08-15 | 河南省化工研究所有限责任公司 | Refining recovery method for dehydrating waste dichloromethane through supergravity coupling membrane |
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